US3959306A - Azolindolines and azolindoline dyestuffs - Google Patents

Azolindolines and azolindoline dyestuffs Download PDF

Info

Publication number
US3959306A
US3959306A US05/446,892 US44689274A US3959306A US 3959306 A US3959306 A US 3959306A US 44689274 A US44689274 A US 44689274A US 3959306 A US3959306 A US 3959306A
Authority
US
United States
Prior art keywords
sub
trimethyl
benzoxazolyl
methylene
indoline
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US05/446,892
Inventor
Horst Harnisch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19702044620 external-priority patent/DE2044620A1/en
Application filed by Bayer AG filed Critical Bayer AG
Priority to US05/446,892 priority Critical patent/US3959306A/en
Application granted granted Critical
Publication of US3959306A publication Critical patent/US3959306A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/90—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof
    • D06P1/908—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof using specified dyes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D473/00—Heterocyclic compounds containing purine ring systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
    • C09B23/0058—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof the substituent being CN
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/16—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing hetero atoms
    • C09B23/162—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing hetero atoms only nitrogen atoms
    • C09B23/164—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing hetero atoms only nitrogen atoms containing one nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
    • C09B69/06—Dyestuff salts, e.g. salts of acid dyes with basic dyes of cationic dyes with organic acids or with inorganic complex acids

Definitions

  • Z represents hydrogen or an optionally modified aldehyde group
  • R 1 and R 2 denote alkyl radicals or represent the remaining members of a cycloalkyl radical
  • R 3 denotes an alkyl or aralkyl radical
  • R 4 denotes hydrogen or an alkyl, cycloalkyl or aralkyl radical
  • A represents the remaining members of an aromatic radical
  • modified aldehyde groups there are especially to be understood acetals, hydrates, ammoniates, aminals, bisulphite adducts, azomethines and hydrazones.
  • Possible aromatic radicals of which the remaining members are designated A are both radicals of monocyclic ring systems and radicals of bicyclic ring systems, which can be built up of aromatic-carbocyclic and/or aromatic-heterocyclic rings in any desired fusion arrangement, and which can optionally also contain fused-on partially saturated, fivemembered or six-membered rings.
  • aromatic radicals there may, for example, be mentioned: the radicals of benzene, naphthalene, tetralin, indane, acenaphthene, pyridine, quinoline, pyrimidine, quinoxaline and indazole. Carbocyclic radicals are preferred.
  • aromatic radicals can also possess substituents, such as halogen, cycloalkyl, aralkyl, phenyl, alkyl, alkoxy, alkylsulphonyl, aralkylsulphonyl, dialkylaminosulphonyl, alkoxycarbonyl, dialkylaminocarbonyl and acylamino radicals.
  • alkyl radicals there are preferably to be understood those with 1 to 5 C atoms, which can possess further substituents, such as halogen, hydroxyl and alkoxy.
  • Suitable alkyl radicals of this nature are, for example, methyl, trifluoromethyl, ethyl, chloroethyl, bromoethyl, hydroxyethyl, methoxyethyl, n-propyl, isopropyl and n-, i- and t-butyl.
  • Suitable aralkyl radicals are especially the benzyl radical and the phenylethyl radical.
  • a suitable cycloalkyl radical is, for example, the cyclohexyl radical.
  • Suitable alkoxy radicals are above all those with 1 to 5 C atoms.
  • alkylsulphonyl radicals the methylsulphonyl and ethylsulphonyl radical should especially be mentioned, and as aralykylsulphonyl radicals the benzylsulphonyl radical should especially be mentioned.
  • Suitable dialkylaminosulphonyl and dialkylaminocarbonyl radicals are preferably those which contain methyl and ethyl groups.
  • alkoxycarbonyl radicals the methoxycarbonyl, ethoxycarbonyl and ⁇ -methoxy-ethoxycarbonyl radicals should for example be mentioned.
  • Suitable acylamino radicals are, for example, acetylamino, propionylamino and methylsulphonylamino radicals.
  • R 1 and R 2 are methyl and ethyl radicals.
  • Suitable cycloalkyl radicals which can be formed by R 1 and R 2 together are cyclohexyl and cyclopentyl radicals.
  • Suitable alkyl radicals R 3 and R 4 are, for example, saturated or unsaturated alkyl radicals with 1 to 5 atoms, which can also possess further substituents, such as halogen, hydroxyl, alkoxy, nitrile, alkylcarbonyl, benzoyl and alkoxycarbonyl radicals.
  • Suitable alkyl radicals of this nature are, for example, methyl, ethyl, chloroethyl, bromoethyl, fluoroethyl, cyanoethyl, methoxyethyl, allyl, n-propyl, isopropyl, ⁇ -hydroxybutyl, acetonyl, phenacyl, methoxycarbonylethyl and n-butyl. Methyl and ethyl radicals are preferred.
  • the new azolindolines of the formula (I) are accessible according to various processes.
  • One of these processes is characterised in that azolindolenines of the formula ##SPC4##
  • A, X, R 1 and R 2 have the abovementioned meaning, are first reacted with alkylating agents or aralkylating agents to give compounds of the formula ##SPC5##
  • Y represents the anionic radical originating from the alkylating or aralkylating agent
  • A, X, R 1 , R 2 and R 3 have the abovementioned meaning.
  • an appropriate procedure is to react approximately equimolar amounts of the reactants in a solvent which is inert under the reaction conditions, such as benzene, toluene, chlorobenzene, o-dichloro-benzene, chloroform, carbon tetrachloride, dioxane, ethyl acetate or acetonitrile, with one another at temperatures between 25° and 130°C.
  • a solvent which is inert under the reaction conditions, such as benzene, toluene, chlorobenzene, o-dichloro-benzene, chloroform, carbon tetrachloride, dioxane, ethyl acetate or acetonitrile, with one another at temperatures between 25° and 130°C.
  • Suitable azolindolenines of the formula (II) are, for example: 2,3,3-trimethyl-5-[5'-methyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-chloro-benzoxazolyl-(2')]-indolenine, 2-methyl-3,3-diethyl-5-[5'-trifluoromethylbenzoxazolyl-(2')]-indolenine, 2,3-dimethyl-3-ethyl-5-[5'-cyclohexyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-phenyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-methoxy-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl
  • azolindolenines of the formula (II) required as the starting material are for example accessible by condensation of appropriate indolenine-5-carboxylic acids or of their derivatives with o-amino compounds of the formula ##EQU1## wherein
  • a and X have the abovementioned meaning, under the customary conditions of the azole synthesis.
  • azole-5-carboxylic acids instead of the azole-5-carboxylic acids, it is also possible to condense the corresponding indolenine-5-aldehydes with the o-amino compounds of the formula (VI), but in that case it is necessary to subject the corresponding azomethines to a cyclising dehydrogenation in a manner which is in itself known, by means of oxidising agents, such as cupric sulphate, lead tetraacetate, nitrobenzene or chloranil.
  • oxidising agents such as cupric sulphate, lead tetraacetate, nitrobenzene or chloranil.
  • a second method of manufacture by which the compounds of the formula (II) are accessible consists of reacting azolylphenylhydrazines of the formula ##SPC8##
  • R 1 and R 2 have the abovementioned meaning, in the presence of zinc chloride, at elevated temperatures, in a manner which is in itself known.
  • Suitable alkylating agents and aralkylating agents for the conversion, according to the invention, of compounds of the formula (II) into those of the formula (III) are, for example, alkyl halides, such as methyl iodide, ethyl bromide, n-propyl bromide, i-propyl chloride, alkyl bromide, n-butyl bromide and isoamyl chloride, sulphuric acid esters of lower alkanols, such as dimethyl sulphate or diethyl sulphate, aromatic sulphonic acid esters, such as p-toluenesulphonic acid methyl ester and ethyl ester, and m-chlorobenzenesulphonic acid ethyl ester, and substituted alkyl halides, such as ⁇ -chloropropionitrile, 4-hydroxybutyl bromide, phenylethyl bromide, benzy
  • the new methylene bases of the formula (IV) are distinguished in that in contrast to most known 1,3,3-trimethyl-2-methylene-indolines they are not obtained as oils which are sensitive to air, but as crystalline substances of relatively good stability, and can hence be isolated particularly easily and conveniently processed further.
  • the methylene bases of the formula IV can be converted in accordance with formylating methods which are in themselves known into the azolindoline- ⁇ -aldehydes of the formula (V), according to the invention.
  • This reaction can be carried out particularly simply and smoothly if the formulation is carried out according to the Vilsmeier method.
  • Suitable Vilsmeier formylating mixtures are for example obtained if phosphorus oxychloride, phosgene or thionyl chloride are reacted with tertiary formamides, such as dimethylformamide or N-formyl-N-methyl-aniline; a mixture of equimolar amounts of phosphorus oxychloride and dimethylformamide is preferred.
  • Excess dimethylformamide or acetonitrile can for example serve as the solvent and diluent.
  • the reaction temperatures can be varied over a major range without the result being changed significantly.
  • the process is advantageously carried out at between 30° and 85°C, preferably at 35°-60°C.
  • the azolindolines of the formula (I) are valuable new intermediate products for methine dyestuffs, which are distinguished by particularly high colour strength, high clarity, excellent affinity, outstanding fastness to sublimation and very good fastness to light, rubbing perspiration and washing, these being properties which the methine dyestuffs hitherto proposed do not possess to the same extent.
  • W 1 represents hydrogen, alkyl, cyclohexyl, phenyl, chlorine, alkoxy, alkylsulphonyl, dialkylaminosulphonyl, alkoxycarbonyl or acylamino and
  • W 2 represents hydrogen or alkyl, with the alkyl and alkoxy radicals having 1 to 5 C atoms, and
  • W 1 and W 2 can additionally together represent the remaining members of a fused 5-membered or 6-membered cycloaliphatic ring or of a benzene ring,
  • W 3 and W 4 independently of one another represent methyl or ethyl groups
  • R denotes an alkyl radical
  • Z denotes hydrogen or an aldehyde group.
  • a further subject of the present invention are azolindoline dyestuffs of the general formula ##SPC10##
  • R 1 and R 2 denote alkyl radicals or represent the remaining members of a cycloalkyl radical
  • R 3 denotes an alkyl or aralkyl radical
  • R 5 denotes an alkyl or aralkyl radical
  • R 4 denotes hydrogen or an alkyl, cycloalkyl or aralkyl radical
  • A represents the remaining members of an aromatic radical, as well as processes for their manufacture and their use.
  • alkyl radicals R 5 there should preferably be mentioned those with 1 to 5 C atoms, which can possess further substituents, such as halogen, hydroxyl, alkoxy and nitrile.
  • Suitable alkyl radicals of this nature are, for example, methyl, ethyl, chloroethyl, hydroxyethyl, methoxyethyl, cyanoethyl, n-propyl, isopropyl and n-, i- and t-butyl, and allyl.
  • Suitable aralkyl radicals R 5 are especially the benzyl radical and the phenylethyl radical.
  • R 5 has the abovementioned meaning.
  • the condensation is carried out in the presence or absence of a solvent or diluent, preferably with the addition of an alkaline catalyst, at elevated temperature, preferably in the range of 60°- 120°C.
  • Suitable solvents or diluents are those which are inert under the conditions of the condensation and are capable of adequately dissolving the reactants, and from which the reaction products separate out well.
  • methanol, ethanol, 2-methoxyethanol, isopropanol, dioxane, benzene, toluene, chlorobenzene, chloroform and pyridine are used.
  • sodium hydroxide, potassium carbonate and sodium acetate should for example be mentioned, secondary organic bases, such as diethylamine, and especially pyrrolidine or piperidine, being preferred.
  • the reactants can be employed in a molar ratio, but an approximately 5% excess of the cyanoacetic acid ester component (3) is advantageous. It is also possible to choose a larger excess of cyanoacetic ester without thereby having an adverse effect on the course of the reaction.
  • Suitable aldehydes of the formula (2) are, for example: 1,3,3-trimethyl-5-[5'-methyl-benzoxazolyl-(2')]-2-methylene-indoline-.omega.-aldehyde, 1-ethyl-3,3dimethyl-5-[5'-chloro-benzoxazolyl-(2)]-2-methylene-iodoline-.omega.-aldehyde, 1-chloroethyl-3,3-dimethyl-5-[5'-trifluoromethyl-benzoxazolyl-(2')]-2-methylene-indoline- ⁇ -aldehyde, 1-n-propyl-3,3-dimethyl-5-[5'-cyclohexyl-benzoxazolyl-(2')]-2-methylene-indoline- ⁇ -aldehyde, 1-allyl-3,3-dimethyl-5-[5'-phenyl-benzoxazo
  • Suitable cyanoacetic acid esters of the formula (3) are, for example: cyanoacetic acid methyl ester, cyanoacetic acid ethyl ester, cyanoacetic acid ⁇ -methoxy-ethyl ester, cyanoacetic acid ⁇ -chloroethyl ester, cyanoacetic acid ⁇ -cyanoethyl ester, cyanoacetic acid ⁇ -hydroxyethyl ester, cyanoacetic acid n-propyl ester, cyanoacetic acid isopropyl ester, cyanoacetic acid allyl ester, cyanoacetic acid n-butyl ester, cyanoacetic acid isobutyl ester, cyanoacetic acid isoamyl ester, cyanoacetic acid benzyl ester, cyanoacetic acid ⁇ -phenylethyl ester and cyanoacetic acid p-methoxy-benzyl ester.
  • W 1 ' represents hydrogen, alkyl, cyclohexyl, phenyl, chlorine, alkoxy, alkylsulphonyl, dialkylaminosulphonyl, alkoxycarbonyl or acylamino and
  • W 2 ' represents hydrogen or alkyl, with the alkyl and alkoxy radicals having 1 - 5 C atoms, and
  • W 1 ' and W 2 ' can additionally together represent the remaining members of a fused 5-membered or 6-membered cycloaliphatic ring or of a benzene ring,
  • W 3 ' and W 4 ' independently of one another represent methyl or ethyl groups
  • Z denotes hydrogen or an aldehyde group
  • R' and R 5 ' each individually denote an alkyl radical with 1 - 5 C atoms.
  • the new azolindoline dyestuffs of the formula (1) are in particular suitable for dyeing and printing synthetic fiber materials and fabric materials such as, for example, polyesters, but preferably materials of synthetic polyamides and polyurethanes.
  • dyestuffs produce, on the fibers and fabrics mentioned, extrordinarily brilliant dyeings in yellow shades, which are distinguished by particularly high colour strength, very good build-up capacity and affinity and excellent fastness properties, such as fastness to washing, rubbing, sublimation, perspiration, exhaust gas and light.
  • the new dyestuffs of the formula (1) can be used for dyeing and printing in accordance with customary processes, for example in the form of aqueous dispersions or printing pastes.
  • the dyebaths and printing pastes can contain the customary dyeing auxiliary additives, such as levelling agents, dispersing agents and dyeing accelerators.
  • the new dyestuffs can also be dyed advantageously from organic solutions, for example from solutions in which solvents which are immiscible with water are used, such as tetrachloroethylene, trichloroethylene, 1,1,2-trichloroethane or 1,1,1-trichloropropane.
  • a mixture of 260 parts of 3-amino-4-hydroxy-toluene, 406 parts of 2,3,3-trimethyl-indolenine-5-carboxylic acid and 20 parts of boric acid is heated for 1 hour to 180° - 190° in a slight stream of nitrogen, whilst distilling off some liquid, and is subsequently heated for a further 40 minutes to 230°.
  • the melt is then fractionally distilled in vacuo, whereupon first of all the water formed and excess 3-amino-4-hydroxy-toluene pass over under a waterpump vacuum. Thereafter, the following fractions are obtained:
  • the main fraction solidifies in the receiver to give a yellowish, crystalline mass and can be further processed without additional purification.
  • a sample recrystallised from alcohol melts at 160° - 162° and corresponds to the formula ##SPC13##
  • Quaternisations of 1a with n-propyl bromide, i-propyl chloride, allyl bromide, n-butyl bromide, isoamyl chloride, chloropropionitrile, chloroacetic acid methyl ester, ⁇ -chloropropionic acid ethyl ester and benzyl chloride are carried out in an autoclave at 120° - 160°.
  • a mixture of 260 parts of 3-amino-4-hydroxy-toluene, 406 parts of 2,3,3-trimethyl-indolenine- 5-carboxylic acid and 20 parts of boric acid is heated for 1 hour to 180° - 190° in a slight stream of nitrogen, whilst distilling off some liquid, and is subsequently further heated to 240° for 40 minutes. Water and excess 3-amino-4-hydroxy-toluene are then distilled off in a waterpump vacuum, under nitrogen, whilst increasing the internal temperature of the melt to 250°.
  • the fabric is introduced at 40°, using a liquor ratio of 1:40 to 1:30, into a dyebath which contains the finely divided dyestuff and 1 g per liter of a conventional anionic dispersing agent.
  • the liquor temperature is raised to 98° (boiling point) over the course of 40 to 60 minutes, and is left at this temperature for about a further 60 minutes.
  • the fabric is rinsed and dried. Strong greenish-tinged yellow dyeings of high clarity and excellent fastness properties are obtained.
  • Dyeings with similar valuable properties are obtained if instead of the dyestuff of the formula 1b one of the dyestuffs listed in Tables 1 and 2 of Example 1b are employed.
  • the fabric is introduced at 50°, using a liquor ratio of 1:40, into a dyebath which contains the finely divided dyestuff, 1 g/l of a conventional anionic dispersing agent, 5 g/l of o- cresotinic acid methyl ester and 1 g/l of NaH 2 PO 4 , and is adjusted to pH 4.5-5 with acetic acid.
  • the temperature is raised to 80°-85° over the course of 20 minutes and the bath is left in this temperature range for a further 20 minutes. Thereafter the liquor is gradually brought to the boil. After a period of boiling of about 1 hour, the dyeing process is complete. After rinsing and drying, greenish-tinged yellow dyeings of high clarity and very good fastness properties are obtained.
  • a knitted fabric of polyhexamethylenediamine adipate filaments is impregnated at room temperature with a solution which contains 6 parts of the dyestuff of the formula 10b (Example 1b, Table 1) and 7 parts of nonylphenol-heptaglycolether in 989 parts of tetrachloroethylene. After squeezing out to a weight increase of 60%, the knitted fabric is dried for one minute at 80°. Thereafter the dyestuff is fixed by heating the knitted fabric to 192° for 45 seconds. Small amounts of dyestuff which have not been fixed are then eluted by brief rinsing in cold tetrachloroethylene. After drying, a very clear, greenish-tinged yellow dyeing is obtained, which is distinguished by its high dyestuff yield, very good build-up and excellent fastness properties.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Indole Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Azolindolines of the formula WHEREIN Z represents hydrogen or an optionally modified aldehyde group, R1 and R2 denote alkyl or represent the remaining members of a cycloalkyl radical, R3 denotes alkyl or aralkyl, X represents oxygen, sulphur or -NR4, wherein R4 denotes hydrogen or alkyl, cycloalkyl or aralkyl, and A represents the remaining members of an aromatic radical, AS WELL AS THEIR PREPARATION, AND, MOREOVER, COMPOUNDS OF THE FORMULA WHEREIN A, X, R1, R2 and R3 have the same meaning as above and R5 denotes alkyl or aralkyl as well as their preparation and their use for the dyeing of synthetic fibre materials.

Description

This is a division of application Ser. No. 179,181 filed Sept. 9, 1971, now U.S. Pat. No. 3,840,552.
The subject of the present invention are azolindolines of the general formula ##SPC3##
Wherein
Z represents hydrogen or an optionally modified aldehyde group,
R1 and R2 denote alkyl radicals or represent the remaining members of a cycloalkyl radical,
R3 denotes an alkyl or aralkyl radical,
X represents oxygen, sulphur or =NR4,
wherein
R4 denotes hydrogen or an alkyl, cycloalkyl or aralkyl radical, and
A represents the remaining members of an aromatic radical,
As well as processes for their manufacture.
By modified aldehyde groups there are especially to be understood acetals, hydrates, ammoniates, aminals, bisulphite adducts, azomethines and hydrazones.
Possible aromatic radicals of which the remaining members are designated A, are both radicals of monocyclic ring systems and radicals of bicyclic ring systems, which can be built up of aromatic-carbocyclic and/or aromatic-heterocyclic rings in any desired fusion arrangement, and which can optionally also contain fused-on partially saturated, fivemembered or six-membered rings.
As examples of such aromatic radicals there may, for example, be mentioned: the radicals of benzene, naphthalene, tetralin, indane, acenaphthene, pyridine, quinoline, pyrimidine, quinoxaline and indazole. Carbocyclic radicals are preferred.
These aromatic radicals can also possess substituents, such as halogen, cycloalkyl, aralkyl, phenyl, alkyl, alkoxy, alkylsulphonyl, aralkylsulphonyl, dialkylaminosulphonyl, alkoxycarbonyl, dialkylaminocarbonyl and acylamino radicals.
By the abovementioned alkyl radicals there are preferably to be understood those with 1 to 5 C atoms, which can possess further substituents, such as halogen, hydroxyl and alkoxy. Suitable alkyl radicals of this nature are, for example, methyl, trifluoromethyl, ethyl, chloroethyl, bromoethyl, hydroxyethyl, methoxyethyl, n-propyl, isopropyl and n-, i- and t-butyl.
Suitable aralkyl radicals are especially the benzyl radical and the phenylethyl radical.
A suitable cycloalkyl radical is, for example, the cyclohexyl radical. Suitable alkoxy radicals are above all those with 1 to 5 C atoms. As alkylsulphonyl radicals, the methylsulphonyl and ethylsulphonyl radical should especially be mentioned, and as aralykylsulphonyl radicals the benzylsulphonyl radical should especially be mentioned. Suitable dialkylaminosulphonyl and dialkylaminocarbonyl radicals are preferably those which contain methyl and ethyl groups.
As alkoxycarbonyl radicals, the methoxycarbonyl, ethoxycarbonyl and β-methoxy-ethoxycarbonyl radicals should for example be mentioned.
Suitable acylamino radicals are, for example, acetylamino, propionylamino and methylsulphonylamino radicals.
Preferred alkyl radicals R1 and R2 are methyl and ethyl radicals. Suitable cycloalkyl radicals which can be formed by R1 and R2 together are cyclohexyl and cyclopentyl radicals.
Suitable alkyl radicals R3 and R4 are, for example, saturated or unsaturated alkyl radicals with 1 to 5 atoms, which can also possess further substituents, such as halogen, hydroxyl, alkoxy, nitrile, alkylcarbonyl, benzoyl and alkoxycarbonyl radicals. Suitable alkyl radicals of this nature are, for example, methyl, ethyl, chloroethyl, bromoethyl, fluoroethyl, cyanoethyl, methoxyethyl, allyl, n-propyl, isopropyl, δ-hydroxybutyl, acetonyl, phenacyl, methoxycarbonylethyl and n-butyl. Methyl and ethyl radicals are preferred.
The new azolindolines of the formula (I) are accessible according to various processes. One of these processes is characterised in that azolindolenines of the formula ##SPC4##
wherein
A, X, R1 and R2 have the abovementioned meaning, are first reacted with alkylating agents or aralkylating agents to give compounds of the formula ##SPC5##
wherein
A, X, R1, R2 and R3 have the abovementioned meaning and
Y represents the anionic radical originating from the alkylating or aralkylating agent,
these are converted in a manner which is in itself known, under alkaline conditions, into the azolindolines of the formula ##SPC6##
wherein
A, X, R1, R2 and R3 have the abovementioned, meaning, and these are, if desired, reacted according to formylation methods which are in themselves known to give aldehydes of the formula ##SPC7##
wherein
A, X, R1, R2 and R3 have the abovementioned meaning.
It must be described as distinctly surprising that the reaction, according to the invention, of (II) with alkylating agents to give (III) takes place selectively at the indolenine nitrogen and that practically no quaternisation of the azole nitrogen occurs. This unforeseeable effect is of decisive importance because with quaternary azoles there is the danger, especially under alkaline conditions, of hydrolytic ring opening.
In carrying out the quaternisation, an appropriate procedure is to react approximately equimolar amounts of the reactants in a solvent which is inert under the reaction conditions, such as benzene, toluene, chlorobenzene, o-dichloro-benzene, chloroform, carbon tetrachloride, dioxane, ethyl acetate or acetonitrile, with one another at temperatures between 25° and 130°C.
Suitable azolindolenines of the formula (II) are, for example: 2,3,3-trimethyl-5-[5'-methyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-chloro-benzoxazolyl-(2')]-indolenine, 2-methyl-3,3-diethyl-5-[5'-trifluoromethylbenzoxazolyl-(2')]-indolenine, 2,3-dimethyl-3-ethyl-5-[5'-cyclohexyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-phenyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-methoxy-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5',6'-dimethyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-bromo-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-tertiary-butyl-benzoxazolyl-(2')]-indolenine, 2,3,3-tri-methyl-5-[5'-fluoro-benzoxazolyl-(2')]-indolenine, 2,3,3-tri-methyl-5-[5'-ethyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-ethylsulphonyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-dimethylaminosulphonyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-β-bromoethyl-benz-oxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-acetylamino-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-β-hydroxyethyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-benzyl-benzoxazolyl-(2')]-indolenine, 2-methyl-3,3-pentamethylene-5-benzoxazolyl-(2')-indolenine, 2,3,3-trimethyl-5-[5'-β-phenylethyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-β-chloroethyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-methylsulphonyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-diethylaminosulphonyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-methyl-sulphonylamino-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-benzylsulphonyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-β-methoxyethyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-diethylaminocarbonyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-methoxy-carbonyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-β-methoxy-ethoxycarbonyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-propionylamino-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl- 5-[5',6'-tetramethylene-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5',6'-trimethylene-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-naphth(1,2-d)-oxazolyl-(2')-indolenine, 2,3,3-trimethyl-5-oxazolo(5,4-b)-pyridine-(2')-indolenine, 2,3,3-trimethyl-5-oxazolo(4,5-g)-quinoline-(2')-indolenine, 2,3,3-trimethyl-5-oxazolo(4,5-c)-quinoline-(2')-indolenine, 2,3,3-trimethyl-5-oxazolo(4,5-d)-pyridazine-(2')-indolenine, 2,3,3-trimethyl-5-oxazolo(4,5-d)-quinoxaline-(2')-indolenine, 2,3,3-trimethyl-5-oxazolo(5,4-d)-pyrimidine-(2')-indolenine, 2,3,3-trimethyl-5-acenaphth(5,4-d)-oxazolyl-(8')-indolenine, 2,3,3-trimethyl-5-benzimidazolyl-(2')-indolenine, 2,3,3-trimethyl-5-[1'-methyl-benzimidazolyl-(2')]-indolenine, 2-methyl-3,3-diethyl-5-[1'-ethyl-5'-methyl-benzimidazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-ethoxy-benzimidazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-imidazolo-(5,4-d)pyrimidine-(2')-indolenine, 2,3,3-trimethyl5-[6'-methyl-benzthiazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[6'-methoxy-benzthiazolyl-(2')]-indolenine and 2,3,3-trimethyl-5-[ 5'-chloro-benzthiazolyl-(2')]-indolenine.
The azolindolenines of the formula (II) required as the starting material are for example accessible by condensation of appropriate indolenine-5-carboxylic acids or of their derivatives with o-amino compounds of the formula ##EQU1## wherein
A and X have the abovementioned meaning, under the customary conditions of the azole synthesis.
Instead of the azole-5-carboxylic acids, it is also possible to condense the corresponding indolenine-5-aldehydes with the o-amino compounds of the formula (VI), but in that case it is necessary to subject the corresponding azomethines to a cyclising dehydrogenation in a manner which is in itself known, by means of oxidising agents, such as cupric sulphate, lead tetraacetate, nitrobenzene or chloranil.
A second method of manufacture by which the compounds of the formula (II) are accessible consists of reacting azolylphenylhydrazines of the formula ##SPC8##
in which
A and X have the abovementioned meaning, with ketones of the formula ##EQU2## in which
R1 and R2 have the abovementioned meaning, in the presence of zinc chloride, at elevated temperatures, in a manner which is in itself known.
Suitable alkylating agents and aralkylating agents for the conversion, according to the invention, of compounds of the formula (II) into those of the formula (III) are, for example, alkyl halides, such as methyl iodide, ethyl bromide, n-propyl bromide, i-propyl chloride, alkyl bromide, n-butyl bromide and isoamyl chloride, sulphuric acid esters of lower alkanols, such as dimethyl sulphate or diethyl sulphate, aromatic sulphonic acid esters, such as p-toluenesulphonic acid methyl ester and ethyl ester, and m-chlorobenzenesulphonic acid ethyl ester, and substituted alkyl halides, such as β-chloropropionitrile, 4-hydroxybutyl bromide, phenylethyl bromide, benzyl chloride, p-chlorobenzyl chloride, p-methoxybenzyl chloride, p-cyanobenzyl chloride, phenylacyl chloride, chloroacetic acid methyl ester, β-chloropropionic acid ethyl ester and β-bromopropionic acid dimethylamide. Dimethyl sulphate and diethyl sulphate are particularly preferred.
The liberation of the azolindolenine-methylene bases of the formula (IV) from the corresponding salts of the formula (III) is achieved in a manner which is in itself known by dissolving the salts of the formula (III), for example in water, and precipitating the methylene base by adding alkali.
The new methylene bases of the formula (IV) are distinguished in that in contrast to most known 1,3,3-trimethyl-2-methylene-indolines they are not obtained as oils which are sensitive to air, but as crystalline substances of relatively good stability, and can hence be isolated particularly easily and conveniently processed further.
The methylene bases of the formula IV can be converted in accordance with formylating methods which are in themselves known into the azolindoline-ω-aldehydes of the formula (V), according to the invention. This reaction can be carried out particularly simply and smoothly if the formulation is carried out according to the Vilsmeier method. Suitable Vilsmeier formylating mixtures are for example obtained if phosphorus oxychloride, phosgene or thionyl chloride are reacted with tertiary formamides, such as dimethylformamide or N-formyl-N-methyl-aniline; a mixture of equimolar amounts of phosphorus oxychloride and dimethylformamide is preferred. Excess dimethylformamide or acetonitrile can for example serve as the solvent and diluent. The reaction temperatures can be varied over a major range without the result being changed significantly. The process is advantageously carried out at between 30° and 85°C, preferably at 35°-60°C.
The azolindolines of the formula (I) are valuable new intermediate products for methine dyestuffs, which are distinguished by particularly high colour strength, high clarity, excellent affinity, outstanding fastness to sublimation and very good fastness to light, rubbing perspiration and washing, these being properties which the methine dyestuffs hitherto proposed do not possess to the same extent.
A particularly valuable class of azolindolines within the framework of the formula (I) corresponds to the formula ##SPC9##
wherein
W1 represents hydrogen, alkyl, cyclohexyl, phenyl, chlorine, alkoxy, alkylsulphonyl, dialkylaminosulphonyl, alkoxycarbonyl or acylamino and
W2 represents hydrogen or alkyl, with the alkyl and alkoxy radicals having 1 to 5 C atoms, and
W1 and W2 can additionally together represent the remaining members of a fused 5-membered or 6-membered cycloaliphatic ring or of a benzene ring,
W3 and W4 independently of one another represent methyl or ethyl groups,
R denotes an alkyl radical and
Z denotes hydrogen or an aldehyde group.
A further subject of the present invention are azolindoline dyestuffs of the general formula ##SPC10##
wherein
R1 and R2 denote alkyl radicals or represent the remaining members of a cycloalkyl radical,
R3 denotes an alkyl or aralkyl radical,
R5 denotes an alkyl or aralkyl radical,
X represents oxygen, sulphur or =NR4,
wherein
R4 denotes hydrogen or an alkyl, cycloalkyl or aralkyl radical, and
A represents the remaining members of an aromatic radical, as well as processes for their manufacture and their use.
The more exact meaning of the radicals R1, R.sub. 2, R3, R4 and A has been given above.
Amongst the alkyl radicals R5, there should preferably be mentioned those with 1 to 5 C atoms, which can possess further substituents, such as halogen, hydroxyl, alkoxy and nitrile. Suitable alkyl radicals of this nature are, for example, methyl, ethyl, chloroethyl, hydroxyethyl, methoxyethyl, cyanoethyl, n-propyl, isopropyl and n-, i- and t-butyl, and allyl.
Suitable aralkyl radicals R5 are especially the benzyl radical and the phenylethyl radical.
The new azolindoline dyestuffs of the formula (1) are obtained if aldehydes of the formula ##SPC11##
wherein
A, X, R1, R2 and R3 have the abovementioned meaning, are condensed with a cyanoacetic acid ester of the formula ##EQU3## wherein
R5 has the abovementioned meaning.
The condensation is carried out in the presence or absence of a solvent or diluent, preferably with the addition of an alkaline catalyst, at elevated temperature, preferably in the range of 60°- 120°C.
Suitable solvents or diluents are those which are inert under the conditions of the condensation and are capable of adequately dissolving the reactants, and from which the reaction products separate out well. For example, methanol, ethanol, 2-methoxyethanol, isopropanol, dioxane, benzene, toluene, chlorobenzene, chloroform and pyridine are used.
As alkaline catalysts, sodium hydroxide, potassium carbonate and sodium acetate should for example be mentioned, secondary organic bases, such as diethylamine, and especially pyrrolidine or piperidine, being preferred.
The reactants can be employed in a molar ratio, but an approximately 5% excess of the cyanoacetic acid ester component (3) is advantageous. It is also possible to choose a larger excess of cyanoacetic ester without thereby having an adverse effect on the course of the reaction.
Suitable aldehydes of the formula (2) are, for example: 1,3,3-trimethyl-5-[5'-methyl-benzoxazolyl-(2')]-2-methylene-indoline-.omega.-aldehyde, 1-ethyl-3,3dimethyl-5-[5'-chloro-benzoxazolyl-(2)]-2-methylene-iodoline-.omega.-aldehyde, 1-chloroethyl-3,3-dimethyl-5-[5'-trifluoromethyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1-n-propyl-3,3-dimethyl-5-[5'-cyclohexyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1-allyl-3,3-dimethyl-5-[5'-phenyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1-n-butyl-3,3-dimethyl-5-[5'-methoxy-benoxazolyl-(2')]-2-methylene-indoline-107 -aldehyde, 1-methyl-3,3-pentamethylene-5-benzoxazolyl-(2')-2-methylene-indoline-.omega.-aldehyde, 1-cyanoethyl-3,3-dimethyl-5-[5',6'-dimethyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1-benzyl-3,3-dimethyl-5-[5'-bromobenzoxazolyl-(2')]-2-methylene-indoline-.omega.-aldehyde, 1-β-phenylethyl-3,3-diethyl-5-[5'-tertiary-butyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1-p-chlorobenzyl-3,3-dimethyl-5-[5'-fluoro-benzoxazolyl-(2')] -2-methylene-indoline-ω-aldehyde, 1-methoxy-carbonylmethyl-3,3-dimethyl-5-[5'-ethylbenzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1-β-ethoxycarbonylethyl-3,3-dimethyl-5-[5'-ethylsulphonyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1-β-dimethylaminocarbonylethyl-3,3-dimethyl-5-[5'-dimethylaminosulphonyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-[5'-β-bromoethyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-[5'-acetylamino-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-[5'-chloroethyl-benzoxazolyl-(2')]-2-methlyene-indoline-ω-aldehyde, 1,3,3-tri-methyl-5-[5'-benzyl-benzoxazolyl-(2' )]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-β-[5'β-phenylethyl-benzoxazolyl-(2')-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-[5'-methoxycarbonyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-[5'-diethylamino-carbonyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-[5'-β-methoxy-ethoxycarbonyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-[5',6'-tetramethylene-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-[5', 6'-trimethylene-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3trimethyl-5-naphth(1,2-d)oxazolyl(2')-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-oxazolo(5,4-b)pyridine-(2')-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-oxazolo(4,5-g)-quinoline-(2')-2-methylene-indoline-.omega.-aldehyde, 1,3,3-trimethyl-5-oxazolo(4,5-d)pyridazine-(2')-2-methylene-indoline-.omega.-aldehyde, 1,3,3-trimethyl-5-oxazolo(4,5-d)quinoxaline-(2')-2-methylene-indoline-.omega.-aldehyde, 1,3,3-trimethyl-5-oxazolo-(5,4-d)pyrimidine-(2')-2-methylene-indoline-.omega.-aldehyde, 1,3,3-trimethyl-5-acenaphth(5,4-d)oxazolyl-(8')-2-methylene-indoline-.omega.-aldehyde, 1,3,3-trimethyl-5-[1'-methyl-benzimidazolyl-(2')]-2-methylene-indoline-.omega.-aldehyde, 1,3,3-triethyl-5-[1'-β-cyanoethyl-5'-methyl-benzimidazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5 -[5'-ethoxy-1'-benzimidazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-imidazolo(5,4-d)pyrimidine-(2')-2-methylene-indoline-.omega.-aldehyde, 1,3,3-trimethyl-5-[6'-methyl-benzthiazolyl-(2')]-2-methylene-indoline-.omega.-aldehyde, 1,3,3-trimethyl-5-[6'-methoxy-benzthiazolyl-(2')]-2-methylene-indoline-.omega.-aldehyde and 1,3,3-triethyl-5-[5'-chloro-benzthiazolyl-(2')-2-methylene-indoline-.omega.-aldehyde.
Suitable cyanoacetic acid esters of the formula (3) are, for example: cyanoacetic acid methyl ester, cyanoacetic acid ethyl ester, cyanoacetic acid β-methoxy-ethyl ester, cyanoacetic acid β-chloroethyl ester, cyanoacetic acid β-cyanoethyl ester, cyanoacetic acid β-hydroxyethyl ester, cyanoacetic acid n-propyl ester, cyanoacetic acid isopropyl ester, cyanoacetic acid allyl ester, cyanoacetic acid n-butyl ester, cyanoacetic acid isobutyl ester, cyanoacetic acid isoamyl ester, cyanoacetic acid benzyl ester, cyanoacetic acid β-phenylethyl ester and cyanoacetic acid p-methoxy-benzyl ester.
A particularly valuable class of azolindoline dyestuffs within the framework of the formula (I) corresponds to the formula ##SPC12##
wherein
W1 ' represents hydrogen, alkyl, cyclohexyl, phenyl, chlorine, alkoxy, alkylsulphonyl, dialkylaminosulphonyl, alkoxycarbonyl or acylamino and
W2 ' represents hydrogen or alkyl, with the alkyl and alkoxy radicals having 1 - 5 C atoms, and
wherein
W1 ' and W2 ' can additionally together represent the remaining members of a fused 5-membered or 6-membered cycloaliphatic ring or of a benzene ring,
W3 ' and W4 ' independently of one another represent methyl or ethyl groups,
Z denotes hydrogen or an aldehyde group and
R' and R5 ' each individually denote an alkyl radical with 1 - 5 C atoms.
The new azolindoline dyestuffs of the formula (1) are in particular suitable for dyeing and printing synthetic fiber materials and fabric materials such as, for example, polyesters, but preferably materials of synthetic polyamides and polyurethanes.
These dyestuffs produce, on the fibers and fabrics mentioned, extrordinarily brilliant dyeings in yellow shades, which are distinguished by particularly high colour strength, very good build-up capacity and affinity and excellent fastness properties, such as fastness to washing, rubbing, sublimation, perspiration, exhaust gas and light.
The yellow dyestuffs hitherto proposed do not possess these advantageous properties to the same extent. As against the nearest comparable methine dyestuffs (German Pat. No. 1,172,387 and French Pat. 1,460,912) the significantly higher colour strength, the better clarity of shade, the beter affinity and the beter fastness to sublimation on polyamides should be singled out.
The new dyestuffs of the formula (1) can be used for dyeing and printing in accordance with customary processes, for example in the form of aqueous dispersions or printing pastes. The dyebaths and printing pastes can contain the customary dyeing auxiliary additives, such as levelling agents, dispersing agents and dyeing accelerators.
The new dyestuffs can also be dyed advantageously from organic solutions, for example from solutions in which solvents which are immiscible with water are used, such as tetrachloroethylene, trichloroethylene, 1,1,2-trichloroethane or 1,1,1-trichloropropane.
The parts indicated in the Examples which follow are parts be weight unless otherwise indicated, and the degrees of temperature indicated are degrees centigrade.
EXAMPLE 1a
A mixture of 260 parts of 3-amino-4-hydroxy-toluene, 406 parts of 2,3,3-trimethyl-indolenine-5-carboxylic acid and 20 parts of boric acid is heated for 1 hour to 180° - 190° in a slight stream of nitrogen, whilst distilling off some liquid, and is subsequently heated for a further 40 minutes to 230°. The melt is then fractionally distilled in vacuo, whereupon first of all the water formed and excess 3-amino-4-hydroxy-toluene pass over under a waterpump vacuum. Thereafter, the following fractions are obtained:
First runnings: 30 parts, 130-170°/2.5 mm Hg.                      
Main fraction: 420 parts, 170-240°/0.1 mm Hg (bath tempera-        
ture not exceeding 270°).
The main fraction solidifies in the receiver to give a yellowish, crystalline mass and can be further processed without additional purification. A sample recrystallised from alcohol melts at 160° - 162° and corresponds to the formula ##SPC13##
Using the appropriate starting materials, the following compounds are obtained analogously: 2,3,3-trimethyl-5-[5'-chloro-benzoxazolyl-(2')]-indolenine, 2-methyl-3,3-diethyl-5-[5'-trifluoromethyl-benzoxazolyl-(2')]-indolenine, 2,3-dimethyl-3-ethyl-5-[5'-cyclohexyl-benzoxazolyl-(2')]-indolenine 2,3,3-trimethyl-5-[5'-phenyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-methoxy-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5',6'-dimethyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-bromobenzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-tertiary-butyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-fluoro-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-ethyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-ethyl-sulphonyl-benzoxazolyl-(2')]-indolenine. 2,3,3-trimethyl-5-[5'-dimethylaminosulphonyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-β-bromoethyl-benzoxazolyl-(2')-indolenine, 2,3,3-trimethyl-5-[5'-acetylamino-benzoxazolyl-(2')]-indolenine, 2,3,3 -trimethyl-5-[5'-β-hydroxyethyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-benzyl-benzoxazolyl-(2')]-indolenine, 2-methyl-3,3-pentamethylene-5-benzoxazolyl-(2')-indolenine, 2,3,3-trimethyl-5-[5'-β-phenylethyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-β-chloroethyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-methyl-sulphonyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[ 5'-diethylaminosulphonyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-methylsulphonylamino-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-benzylsulphonyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-β-methoxyethyl-benzoxazolyl-(2')-indolenine, 2,3,3-trimethyl-5-[5'-diethyl-aminocarbonyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5[5'-methoxycarbonyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-β-methoxy-ethoxycarbonyl-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5'-propionylamino-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-[5', 6'-tetramethylene-benzoxazolyl-(2')]-indolenine, 2,3,3-trimethyl- 5-[5', 6'-trimethylene-benzoxazolyl-(2')]-indolenine, 2,3,3trimethyl-5-naphth(1,2-d)oxazolyl-(2')-indolenine, 2,3,3-trimethyl-5-oxazolo(5,4-b)pyridine-(2')-indolenine, 2,3,3-trimethyl-5-oxazolo(4,5-g)quinoline-(2')-indolenine, 2,3,3-trimethyl-5-oxazolo(4,5-c)quinoline-(2'-indolenine, 2,3,3-trimethyl-5-oxazolo(4,5-d)pyridazine-(2')-indolenine, 2,3,3-trimethyl-5-oxazolo(4,5-d)quinoxaline-(2')-indolenine, 2,3,3-trimethyl- 5-oxazolo(5,4-d)pyrimidine-(2')-indolenine, 2,3,3-trimethyl-5-acenaphth(5,4-d)oxazolyl-(8')-indolenine, 2,3,3-trimethyl-5-benzimidazolyl-(2')-indolenine, 2,3,3-trimethyl- 5-[1'-methyl-benzimidazolyl-(2')]-indolenine, 2-methyl-3,3-diethyl-5-[1'-ethyl-5'-methyl-benzimidazolyl-(2')]-indolenine, 2,3,3,-trimethyl-5-[5'-ethoxy-benzimidazolyl-(2')]-indolenine, 2,3,3-trimethyl-5-imidazolo(5,4-d)pyrimidine-(2')-indolenine, 2,3,3-trimethyl-5-[6'-methyl-benzthiazolyl-(2')-indolenine, 2,3,3-trimethyl-5-[6'-methoxy-benzthiazolyl-(2')-indolenine and 2,3,3-trimethyl-5-[5'-chloro-benzthiazolyl-(2')-indolenine.
EXAMPLE 2a
419.5 parts of the compound of the formula 1a (main fraction of Example 1a) are dissolved in 2700 parts by volume of chlorobenzene, with warming. 200 parts by volume of chlorobenzene are then distilled off in a waterpump vacuum. Thereafter 181 parts of dimethyl sulphate are added dropwise at 50° to 60°, without further heating, and occasional short cooling with cold water may be necessary. When the exothermic reaction has subsided, the batch is further heated to 55° - 60° for 3 hours. After cooling, the crystalline precipitate is filtered off and washed with about 400 parts by volume of chlorobenzene. The resulting compound of the formula ##SPC14##
can be further processed whilst moist with chlorobenzene. If the substance is dried in vacuo at 70° in order to determine the yield, 470 parts of melting point 184° - 192° (decomposition) are obtained. A sample of the substance manufactured from recrystallised intermediate product melts at 283°, with decomposition.
Thereafter, the quaternary salt which is moist with chlorobenzene is dissolved in 5400 parts of water at 40° and the chlorobenzene is distilled off azeotropically in vacuo, until the distillate which passes over is no longer cloudy. The solution is subsequently clarified at 40° with 15 parts of active charcoal, and is filtered. 740 parts of 25% strength sodium hydroxide solution are slowly run into the filtrate, whilst stirring, whereupon an almost colourless, crystalline precipitate separates out. This is filtered off, washed with water until neutral and dried in vacuo at 50° . 243 parts of the compound of the formula ##SPC15##
of melting point 153° - 156° (decomposition) are obtained. Dilute solutions of the substance in organic solvents, such as alcohol, toluene or dimethylformamide show a strong blue fluorescence. In contrast to most known 1,3,3-trimethyl-2-methylene-indolines, this compound has relatively good stability to atmospheric oxygen.
If, instead of dimethyl sulphate, an equimolar amount of diethyl sulphate is employed and the quaternisation is carried out for 10 hours at 70°, then the compound of the formula ##SPC16##
is obtained in comparable yield after working up under alkaline conditions. If the quaternisation is carried out with p-toluenesulphonic acid methyl ester, p-toluenesulphonic acid ethyl ester or m-chlorobenzenesulphonic acid methyl ester, a reaction temperature of 110° - 120° is required.
Quaternisations of 1a with n-propyl bromide, i-propyl chloride, allyl bromide, n-butyl bromide, isoamyl chloride, chloropropionitrile, chloroacetic acid methyl ester, β-chloropropionic acid ethyl ester and benzyl chloride are carried out in an autoclave at 120° - 160°.
Using the appropriate starting materials, the following compounds are obtained analogously: 1-ethyl-3,3-dimethyl-5-[5'-chloro-benzoxazolyl-(2')]-2-methylene-indoline, 1-ethyl-3,3-dimethyl-5-[5'-cyclohexyl-benzoxazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5-[5'-phenyl-benzoxazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5-[5'-methoxy-benzoxazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5-[5'-bromo-benzoxazolyl-(2')]-2-methylene-indoline, 1-ethyl-3,3-dimethyl-5-[5',6'-dimethyl-benzoxazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5-[5'tertiary-butyl-benzoxazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5-[5'-fluoro-benzoxazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl- 5-[5'-ethyl-benzoxazolyl-(2')]-2-methylene-indoline, 1-ethyl-2,3-dimethyl-5-[5'-ethylsulphonyl-benzoxazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5-[5'-dimethylaminosulphonyl-benzoxazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5[5'-methoxy-carbonyl-benzoxazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5-[5'-benzyl-benzoxazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5-[5'-diethylaminocarbonyl-benzoxazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5-[5',6'-tetramethylene-benzoxazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5-[5',6'-trimethylene-benzoxazolyl-(2')]-2-methylene-indoline, 1,3,3-triethyl-5-benzoxazolyl-(2')-2-methylene-indoline, 1-methyl-3,3-pentamethylene-5-benzoxazolyl-(2')-methylene-indoline, 1,3,3-trimethyl-5-[5'-acetylamino-benzoxazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5-[5'-isopropyl-benzoxazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5-[5'-(1",1",3",3"-tetramethyl-n-butyl)-benzoxazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5-[5'-ethoxy-benzoxazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5-[5'-methylamino-sulphonyl-benzoxazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5-[5'-n-propylaminocarbonyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5-naphth(1,2-d)oxazolyl-(2')-2-methylene-indoline, 1,3,3-trimethyl-5-oxazolo(5,4-b)-pyridine-(2')-2-methylene-indoline, 1,3,3-trimethyl-5-oxazolo-(4,5-g)-quinoline-(2')-2-methylene-indoline, 1,3,3-trimethyl-5-oxazolo(4,5-d)pyridazine-(2')-2-methylene-indoline, 1,3,3-trimethyl-5-oxazolo(4,5-d)quinoxaline-(2')-2-methylene-indoline, 1,3,3-trimethyl-5-oxazolo(5,4-d)pyrimidine-(2')-2-methylene-indoline, 1,3,3-trimethyl-5-acenaphth(5,4-d)-oxazolyl-(8')-2-methylene-indoline, 1,3,3-trimethyl-5-[1'-methyl-benzimidazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5-[1'-β-cyanoethyl-5'-methyl-benzimidazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5-[5'ethoxy-1'-ethyl-benzimidazolyl-(2')]-2-methylene-indoline, 1,3,3-trimethyl-5[6'-methyl-benzthiazolyl-(2')-2-methylene-indoline, 1,3,3-trimethyl-5-[6'-methoxy-benzthiazolyl-(2')]-2-methylene-indoline and 1,3,3-trimethyl-5-[5'-chloro-benzthiazolyl-(2')]-2-methylene-indoline.
EXAMPLE 3a
130 g of dimethylformamide are rapidly added dropwise to 150 parts of phosphorus oxychloride at 25° to 50°, whilst cooling with water. The mixture is further warmed to 50° for 1 hour and is treated with 400 parts of acetonitrile. Thereafter 242 parts of the compound of the formula 3a are added over the course of 20 minutes at 50° - 70°, whilst gently cooling with water and stirring, and the reaction mixture is heated for 2 hours to 50° and 4 hours to 70° and poured out, whilst stirring, onto a mixture of 1500 parts of water, 1000 parts of ice and 560 parts of 50% strength sodium hydroxide solution. The mixture is stirred for 5 hours. The crystalline precipitate which forms is then filtered off, washed with water until neutral and dried in vacuo at 70°. 249 parts of the compound of the formula ##SPC17##
of melting point 239° - 241° are obtained.
If the reaction mixture is not poured out onto ice water and sodium hydroxide solution, but only onto ice water, a strongly acid, aqueous solution of the Vilsmeier intermediate product of the formula ##SPC18##
is obtained.
If, instead of the compound of the formula 3a, an equimolar amount of the compound of the formula 4a is employed, 259 parts of the compound of the formula ##SPC19## are obtained.
The following compounds are obtained analogously from the appropriate starting components: 1-ethyl-3,3-dimethyl-5-[5'-chloro-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1-ethyl-3,3-dimethyl-5-[5'-cyclohexyl-benzoxazolyl-(2')-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-[5'-phenyl-benzoxazolyl-(2')]-2-methylene-indoline-.omega.-aldehyde, 1,3,3-trimethyl-5-[5'-methoxy-benzoxazolyl)-(2')]-2-methylene-indoline-.omega.-aldehyde, 1,3,3-trimethyl-5-[5'-bromo-benzoxazolyl-(2')]-2-methylene-indoline-.omega.-aldehyde, 1-ethyl-3,3-dimethyl-5-[5',6'-dimethyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-[5'-tertiary-butyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-[5'-fluoro-benzoxazolyl-(2')]-2-methylene-indoline-.omega.-aldehyde, 1,3,3-trimethyl-5-[5'-ethyl-benzoxazolyl-(2')]-2-methylene-indoline-.omega.-aldehyde, 1-ethyl-2,3-dimethyl-5-[5'-ethylsulphonyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-[5'-dimethylaminosulphonyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-[ 5'-methoxycarbonyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-[5'-benzyl-benzoxazolyl-(2')]-2-methylene-indoline-.omega.-aldehyde, 1,3,3-trimethyl-5-[5'-diethyl-aminocarbonyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-[5',6'-tetramethylene-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-[5',6'-trimethylene-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-triethyl-5-benzoxazolyl-(2')-2-methylene-indoline-ω-aldehyde, 1-methyl-3,3-pentamethylene-5-benzoxazolyl-(2')-2-methylene-indoline-.omega.-aldehye, 1,3,3-trimethyl-5[5'-acetylamino-benzoxazolyl-(2')]-2-methylene-indoline-.omega.-aldehyde, 1,3,3-triethyl-5-[5'-isopropyl-benzoxazolyl-(2')]-2-methylene-indoline-.omega.-aldehye, 1,3,3-trimethyl-5-[5'-(1",1",3",3"-tetramethyl-n-butyl)-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-[5'-ethoxy-benzoxazolyl-(2')]-2-methylene-indoline-.omega.-aldehyde, 1,3,3-trimethyl-5-[5'-methyl-aminosulphonyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-[5'-n-propylaminocarbonyl-benzoxazolyl-(2')]-2-methylene-indoline-ω -aldehyde, 1,3,3-trimethyl-5-naphth(1,2-d)oxazolyl-(2')-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-oxazolo(5,4-b)pyridine-(2')-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-oxazolo(4,5-g)quinoline-(2')-2-methylene-indoline-.omega.-aldehyde, 1,3,3-trimethyl-5-oxazolo(4,5-d)pyridazine-(2')-2-methylene-indoline-.omega.-aldehyde, 1,3,3-trimethyl-5-oxazolo(4,5-d)-quinoxaline-(2')-2-methylene-indoline-.omega.-aldehyde, 1,3,3-trimethyl-5-oxazolo(5,4-d)pyrimidine-(2')-2-methylene-indoline-.differential.-aldehyde, 1,3,3-trimethyl-5-acenaphth(5,4-d)oxazolyl-(8')-2-methylene-indoline-.omega.-aldehye, 1,3,3-trimethyl-5-['-methyl-benzimidazolyl-(2')]-2-methylene-indoline-.omega.-aldehyde, 1,3,3-trimethyl-5-[1'-β-cyanoethyl-5'-methyl-benzimidazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5-[5'-ethoxy-1'-ethyl-benzimidazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1,3,3-trimethyl-5[6'-methyl-benzthiazolyl-(2')]-2-methylene-indoline-.omega.-aldehyde, 1,3,3-trimethyl-5-[6'-methoxy-benzthiazolyl-(2')]-2-methylene-indoline-.omega.-aldehyde, 1,3,3-trimethyl-5-[5'-chloro-benzthiazolyl-(2')]-2-methylene-indoline-.omega.-aldehyde, 1-n-propyl-3,3-dimethyl- 5-[5'-methyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1-n-butyl-3,3-dimethyl-5-[5'-methyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1-β-cyanoethyl-3,3-dimethyl-5-[5'-methyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehye, 1-methoxycarbonylmethyl-3,3-dimethyl-5-[5'-methyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1-β-ethoxycarbonylethyl-3,3-dimethyl-5-[5'-methyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde, 1β-chloro-ethyl-3,3-dimethyl-5-[5'-methyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehye, 1-allyl-3,3-dimethyl-5-[5'-methyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde and 1-benzyl-3,3-dimethyl-5[5'-methyl-benzoxazolyl-(2')]-2-methylene-indoline-ω-aldehyde.
EXAMPLE 4a
A mixture of 260 parts of 3-amino-4-hydroxy-toluene, 406 parts of 2,3,3-trimethyl-indolenine- 5-carboxylic acid and 20 parts of boric acid is heated for 1 hour to 180° - 190° in a slight stream of nitrogen, whilst distilling off some liquid, and is subsequently further heated to 240° for 40 minutes. Water and excess 3-amino-4-hydroxy-toluene are then distilled off in a waterpump vacuum, under nitrogen, whilst increasing the internal temperature of the melt to 250°. After cooling to 150° under nitrogen, 2800 parts by volume of chlorobenzene are added and in order completely to remove the water azeotropically, 200 parts by volume of chlorobenzene are distilled off. 270 parts of dimethyl sulphate are subsequently added dropwise at 60° - 65°, whilst occasionally cooling with cold water. The batch is subsequently heated to 60° - 65° for a further 7 hours whilst stirring, and is then cooled to room temperature. The crystalline precipitate is washed with about 1000 parts by volume of chlorobenzene and then with 300 parts by volume of benzene, and is dried in vacuo at 50°. 745 g of quaternary salt of the formula 2a, of melting point 196° - 198°, are obtained. These are suspended in 1700 parts by volume of dimethylformamide, whilst stirring. 181 parts of triethylamine are added dropwise at 20° - 25° under nitrogen, whilst cooling, whereupon the methylene base of the formula 3a forms. The mixture is then treated dropwise, at 20° - 55°, with 400 parts of phosphorus oxychloride, whilst stirring and cooling with an ice bath. Thereafter the batch is heated to 60° for a further 6 hours, whilst stirring, and is then poured out onto a mixture of 4000 parts of water, 1500 parts of ice and 1550 parts by volume of 50% strength sodium hydroxide solution, whilst stirring. The mixture is stirred for 6 hours at room temperature and the product is filtered off, washed with 6000 parts of water until neutral and dried at 50° in vacuo. 540 parts of aldehyde of the formula 5a are obtained, melting at 240° -242° after recrystallisation from dimethylformamide.
EXAMPLE 1b
102 parts of 1,3,3-trimethyl-5-[5'-methyl-benzoxazolyl-(2')]-2-methylene-indoline-.omega.-aldehyde (compound 5a in Example 3a), 45 parts of cyanoacetic acid ethyl ester and 10 parts of piperidine in 800 parts by volume of ethanol are heated to the boil for 5 hours under reflux, whilst stirring, and are then cooled. The crystalline precipitate which separates out is filtered off, washed with ice-cold methanol and dried at 50° in vacuo. 120 parts of the compound of the formula ##SPC20##
melting at 237° to 239° are obtained. Strongly greenish-tinged, clear yellow on polyamide.
The following dyestuffs are obtained analogously, if the appropriate starting materials are used: ##SPC21##
                                  Table 1                                 
__________________________________________________________________________
                                                    Colour shade          
No.                                                                       
   U.sup.1       U.sup.2                                                  
                     U.sup.3                                              
                        U.sup.4                                           
                            U.sup.5     U.sup.6     on polyamide          
__________________________________________________________________________
 2b                                                                       
   CH.sub.3      H   CH.sub.3                                             
                        CH.sub.3                                          
                            C.sub.2 H.sub.5                               
                                        CH.sub.3    greenish-tinged       
                                                    yellow                
 3b                                                                       
   Cl            H   CH.sub.3                                             
                        CH.sub.3                                          
                            C.sub.2 H.sub.5                               
                                        --CH.sub.2 --CH.sub.2 --OCH.sub.3 
                                                    greenish-tinged       
                                                    yellow                
 4b              H   CH.sub.3                                             
                        CH.sub.3                                          
                            C.sub.2 H.sub.5                               
                                        --CH.sub.2 --CH.sub.2 --CN        
                                                    greenish-tinged       
                                                    yellow                
 CH.sub.3                                                                 
   --CH.sub.2 OCH.sub.3                                                   
                 greenish-tinged yellow                                   
   CH.sub.3                                                               
 5b              H   CH.sub.3                                             
                        CH.sub.3                                          
                            CH.sub.3    --2 --CH.sub.2 --CH.sub.3         
                                                    greenish-tinged       
                                                    yellow                
                                        CH.sub.3                          
 6b                                                                       
   CH.sub.3 O    H   CH.sub.3                                             
                        CH.sub.3                                          
                            CH.sub.3    --CH∠ greenish-tinged       
                                                    yellow                
                                        CH.sub.3                          
 7b                                                                       
   H             CH.sub.3 O                                               
                     CH.sub.3                                             
                        CH.sub.3                                          
                            CH.sub.3    --CH.sub.2 --CH.sub.2 --OH        
                                                    greenish-tinged       
                                                    yellow                
 8b                                                                       
   Br            H   CH.sub.3                                             
                        CH.sub.3                                          
                            CH.sub.3    --CH.sub.2 --CH.sub.2 --Cl        
                                                    greenish-tinged       
                                                    yellow                
 9b                                                                       
   CH.sub.3      CH.sub.3                                                 
                     CH.sub.3                                             
                        CH.sub.3                                          
                            CH.sub.3    --CH.sub.2 --CH=CH.sub.2          
                                                    greenish-tinged       
                                                    yellow                
10b                                                                       
   (CH.sub.3).sub.3 C--                                                   
                 H   CH.sub.3                                             
                        CH.sub.3                                          
                            CH.sub.3    --CH.sub.2 --CH.sub.2 --CH.sub.2  
                                        --CH.sub.3  greenish-tinged       
                                                    yellow                
                                        CH.sub.3                          
11b                                                                       
   F             H   CH.sub.3                                             
                        CH.sub.3                                          
                            CH.sub.3    --CH.sub.2 --CH∠            
                                                    greenish-tinged       
                                                    yellow                
                                        CH.sub.3                          
                                        CH.sub.3                          
12b                                                                       
   C.sub.2 H.sub.5 --                                                     
                 H   CH.sub.3                                             
                        CH.sub.3                                          
                            CH.sub.3    --CH.sub.2 --CH.sub.2 --CH∠ 
                                                    greenish-tinged       
                                                    yellow                
                                        CH.sub.3                          
13b                                                                       
   C.sub.2 H.sub.5 SO.sub.2 --                                            
                 H   CH.sub.3                                             
                        CH.sub.3                                          
                            C.sub.2 H.sub.5                               
                                        --CH.sub.2  greenish-tinged       
                                                    yellow                
   CH.sub.3                                                               
14b                                                                       
   ∠N--SO.sub.2 --                                                  
                 H   CH.sub.3                                             
                        CH.sub.3                                          
                            CH.sub.3                greenish-tinged       
                                                    yellow                
   CH.sub.3                                                               
   O                                                                      
   ∥                                                             
15b                                                                       
   CH.sub.3 O--C--                                                        
                 H   CH.sub.3                                             
                        CH.sub.3                                          
                            CH.sub.3    --CH.sub.2 --CH.sub.2             
                                                    greenish-tinged       
                                                    yellow                
16b              H   CH.sub.3                                             
                        CH.sub.3                                          
                            CH.sub.3    C.sub.2 H.sub.5                   
                                                    greenish-tinged       
                                                    yellow                
   O                                                                      
   C.sub.2 H.sub.5 ∥                                             
17b                                                                       
   ∠N--C-- H   CH.sub.3                                             
                        CH.sub.3                                          
                            CH.sub.3    CH.sub.3    greenish-tinged       
                                                    yellow                
   C.sub.2 H.sub.5                                                        
18b                                                                       
   H             H   C.sub.2 H.sub.5                                      
                        C.sub.2 H.sub.5                                   
                            C.sub.2 H.sub.5                               
                                        C.sub.2 H.sub.5                   
                                                    greenish-tinged       
                                                    yellow                
   O                                                                      
   ∥                           CH.sub.3                          
19b                                                                       
   CH.sub.3 --C--NH--                                                     
                 H   CH.sub.3                                             
                        CH.sub.3                                          
                            CH.sub.3    --CH∠ greenish-tinged       
                                                    yellow                
                                        CH.sub.3                          
   CH.sub.3                                                               
20b                                                                       
   ∠CH--   H   CH.sub.3                                             
                        CH.sub.3                                          
                            CH.sub.3    --CH.sub.2 OCH.sub.3              
                                                    greenish-tinged       
                                                    yellow                
   CH.sub.3 CH.sub.3                                                      
   ||                                                   
21b                                                                       
   CH.sub.3 --C--CH.sub.2 --C--                                           
                 H   CH.sub.3                                             
                        CH.sub.3                                          
                            CH.sub.3    C.sub.2 H.sub.5                   
                                                    greenish-tinged       
                                                    yellow                
   ||                                                   
   CH.sub.3 CH.sub.3                                                      
22b                                                                       
   C.sub.2 H.sub.5 O--                                                    
                 H   CH.sub.3                                             
                        CH.sub.3                                          
                            CH.sub.3    CH.sub.2 --CH.sub.2 --Br          
                                                    greenish-tinged       
                                                    yellow                
23b                                                                       
   CH.sub.3 --SO.sub.2 --NH--                                             
                 H   CH.sub.3                                             
                        CH.sub.3                                          
                            CH.sub.3    C.sub.2 H.sub.5                   
                                                    greenish-tinged       
                                                    yellow                
   O                                                                      
   ∥                                                             
24b                                                                       
   CH.sub.3 --CH.sub.2 --CH.sub.2 --C--NH--                               
                 H   CH.sub.3                                             
                        CH.sub.3                                          
                            CH.sub.3    CH.sub.3    greenish-tinged       
                                                    yellow                
25b                                                                       
   CH.sub.3      H   CH.sub.3                                             
                        CH.sub.3                                          
                            --CH.sub.2 --CH.sub.2 --CH.sub.3              
                                        C.sub.2 H.sub.5                   
                                                    greenish-tinged       
                                                    yellow                
26b                                                                       
   CH.sub.3      H   CH.sub.3                                             
                        CH.sub.3                                          
                            --CH.sub.2 --CH.sub.2 --CH.sub.2 --CH.sub.3   
                                        C.sub.2 H.sub.5                   
                                                    greenish-tinged       
                                                    yellow                
27b                                                                       
   CH.sub.3      H   CH.sub.3                                             
                        CH.sub.3                                          
                            --CH.sub.2 --CH.sub.2 --CN                    
                                        C.sub.2 H.sub.5                   
                                                    greenish-tinged       
                                                    yellow                
                            O                                             
                            ∥                                    
28b                                                                       
   CH.sub.3      H   CH.sub.3                                             
                        CH.sub.3                                          
                            --CH.sub.2 --C--OCH.sub.3                     
                                        C.sub.2 H.sub.5                   
                                                    greenish-tinged       
                                                    yellow                
                            O                                             
                            ∥                                    
29b                                                                       
   CH.sub.3      H   CH.sub.3                                             
                        CH.sub.3                                          
                            --CH.sub.2 --CH.sub.2 --C--OC.sub.2 H.sub.5   
                                        C.sub.2 H.sub.5                   
                                                    greenish-tinged       
                                                    yellow                
30b                                                                       
   CH.sub.3      H   CH.sub.3                                             
                        CH.sub.3                                          
                            --CH.sub.2 --CH.sub.2 --Cl                    
                                        C.sub. 2 H.sub.5                  
                                                    greenish-tinged       
                                                    yellow                
31b                                                                       
   CH.sub.3      H   CH.sub.3                                             
                        CH.sub.3                                          
                            --CH.sub.2 --CH=CH.sub.2                      
                                        C.sub.2 H.sub.5                   
                                                    greenish-tinged       
                                                    yellow                
32b                                                                       
   CH.sub.3      H   CH.sub.3                                             
                        CH.sub.3                                          
                            --CH.sub.2  C.sub.2 H.sub.5                   
                                                    greenish-tinged       
                                                    yellow                
__________________________________________________________________________
 ##SPC22##

                                  Table 2                                 
__________________________________________________________________________
                                          Colour shade                    
No.    U             U.sup.3 U.sup.4                                      
                                  U.sup.5                                 
                                      U.sup.6                             
                                          on polyamide                    
__________________________________________________________________________
33b                  CH.sub.3                                             
                             CH.sub.3                                     
                                  CH.sub.3                                
                                      C.sub.2 H.sub.5                     
                                          greenish-                       
                                          tinged yellow                   
34b                  CH.sub.3                                             
                             CH.sub.3                                     
                                  C.sub.2 H.sub.5                         
                                      CH.sub.3                            
                                          greenish-                       
                                          tinged yellow                   
35b                  CH.sub.3                                             
                             CH.sub.3                                     
                                  CH.sub.3                                
                                      C.sub.2 H.sub.5                     
                                          yellow                          
36b                  CH.sub.3                                             
                             CH.sub.3                                     
                                  CH.sub.3                                
                                      C.sub.2 H.sub.5                     
                                          greenish-                       
                                          tinged yellow                   
37b                  CH.sub.3                                             
                             CH.sub.3                                     
                                  CH.sub.3                                
                                      C.sub.2 H.sub.5                     
                                          yellow                          
38b                  CH.sub.3                                             
                             CH.sub.3                                     
                                  CH.sub.3                                
                                      C.sub.2 H.sub.5                     
                                          greenish-                       
                                          tinged yellow                   
39b                  CH.sub.3                                             
                             CH.sub.3                                     
                                  CH.sub.3                                
                                      C.sub.2 H.sub.5                     
                                          yellow                          
40b                  CH.sub.3                                             
                             CH.sub.3                                     
                                  CH.sub.3                                
                                      C.sub.2 H.sub.5                     
                                          greenish-                       
                                          tinged yellow                   
41b                  CH.sub.3                                             
                             CH.sub.3                                     
                                  CH.sub.3                                
                                      C.sub.2 H.sub.5                     
                                          yellow                          
42b                  --CH.sub.2 --(CH.sub.2).sub.3                        
                             --CH.sub.2 --                                
                                  CH.sub.3                                
                                      C.sub.2 H.sub.5                     
                                          greenish-                       
                                          tinged yellow                   
43b                  CH.sub.3                                             
                             CH.sub.3                                     
                                  CH.sub.3                                
                                      C.sub.2 H.sub.5                     
                                          greenish-                       
                                          tinged yellow                   
44b                  CH.sub.3                                             
                             CH.sub.3                                     
                                  CH.sub.3                                
                                      C.sub.2 H.sub.5                     
                                          greenish-                       
                                          tinged yellow                   
45b                  CH.sub.3                                             
                             CH.sub.3                                     
                                  CH.sub.3                                
                                      C.sub.2 H.sub.5                     
                                          yellow                          
46b                  CH.sub.3                                             
                             CH.sub.3                                     
                                  CH.sub.3                                
                                      C.sub.2 H.sub.5                     
                                          yellow                          
47b                  CH.sub.3                                             
                             CH.sub.3                                     
                                  CH.sub.3                                
                                      C.sub.2 H.sub.5                     
                                          yellow                          
48b                  CH.sub.3                                             
                             CH.sub.3                                     
                                  CH.sub.3                                
                                      C.sub.2 H.sub.5                     
                                          yellow                          
__________________________________________________________________________
EXAMPLE 2b
An approximately 0.1% strength dyeing with dyestuff 1b on polyamide-6 fabrics is produced as follows:
The fabric is introduced at 40°, using a liquor ratio of 1:40 to 1:30, into a dyebath which contains the finely divided dyestuff and 1 g per liter of a conventional anionic dispersing agent. The liquor temperature is raised to 98° (boiling point) over the course of 40 to 60 minutes, and is left at this temperature for about a further 60 minutes. Thereafter, the fabric is rinsed and dried. Strong greenish-tinged yellow dyeings of high clarity and excellent fastness properties are obtained.
Dyeings with similar valuable properties are obtained if instead of the dyestuff of the formula 1b one of the dyestuffs listed in Tables 1 and 2 of Example 1b are employed.
EXAMPLE 3b
An approximately 0.2% strength dyeing with dyestuff 2b on polyethylene terephthalate fabric is produced as follows:
The fabric is introduced at 50°, using a liquor ratio of 1:40, into a dyebath which contains the finely divided dyestuff, 1 g/l of a conventional anionic dispersing agent, 5 g/l of o- cresotinic acid methyl ester and 1 g/l of NaH2 PO4, and is adjusted to pH 4.5-5 with acetic acid. The temperature is raised to 80°-85° over the course of 20 minutes and the bath is left in this temperature range for a further 20 minutes. Thereafter the liquor is gradually brought to the boil. After a period of boiling of about 1 hour, the dyeing process is complete. After rinsing and drying, greenish-tinged yellow dyeings of high clarity and very good fastness properties are obtained.
EXAMPLE 4b
An approximately 0.22% strength dyeing with dyestuff 1b on cellulose triacetate fabric is produced in accordance with the method of dyeing indicated in Example 3b. The resulting strongly greenish-tinged dyeing displays high clarity and good fastness properties.
EXAMPLE 5b
A knitted fabric of polyhexamethylenediamine adipate filaments is impregnated at room temperature with a solution which contains 6 parts of the dyestuff of the formula 10b (Example 1b, Table 1) and 7 parts of nonylphenol-heptaglycolether in 989 parts of tetrachloroethylene. After squeezing out to a weight increase of 60%, the knitted fabric is dried for one minute at 80°. Thereafter the dyestuff is fixed by heating the knitted fabric to 192° for 45 seconds. Small amounts of dyestuff which have not been fixed are then eluted by brief rinsing in cold tetrachloroethylene. After drying, a very clear, greenish-tinged yellow dyeing is obtained, which is distinguished by its high dyestuff yield, very good build-up and excellent fastness properties.

Claims (4)

I claim:
1. Azolindoline dyestuff of the formula ##SPC23##
wherein
W1 is hydrogen, alkyl of 1-5 carbon atoms, cyclo-hexyl, phenyl, chloro, alkoxy of 1-5 carbon atoms, methyl-sulfonyl, ethylsulfonyl, dimethylaminosulfonyl, diethylamino-sulfonyl, dimethylaminocarbonyl, diethylaminocarbonyl, methoxycarbonyl, ethoxycarbonyl, β-methoxyethoxycarbonyl, acetylamino, propionylamino, or methylsulfonylamino;
W2 is hydrogen or alkyl of 1-5 carbon atoms;
W1 and W2 additionally can be joined together to produce a fused benzene ring;
R1 and R2 separately are methyl or ethyl, or can be joined together to produce a cyclopentyl or a cyclohexyl ring;
R3 is alkyl of 1-5 carbon atoms, chloroethyl, bromo-ethyl, fluoroethyl, cyanoethyl, allyl, methoxycarbonylethyl, benzyl, or phenylethyl;
R5 is alkyl of 1-5 carbon atoms, chloroethyl, hydroxy-ethyl, methoxyethyl, cyanoethyl, allyl, benzyl or phenylethyl; and
R4 is hydrogen, alkyl of 1-5 carbon atoms, chloroethyl, bromoethyl, fluoroethyl, cyanoethyl, methoxyethyl, δ-hydroxy-butyl, acetonyl, allyl, methoxycarbonylethyl, benzyl, phenyl-ethyl, or cyclohexyl.
2. The dyestuff of claim 1 having the formula ##SPC24##
3. The dyestuff of claim 1 having the formula ##SPC25##
4. The dyestuff of claim 1 having the formula: ##SPC26##
US05/446,892 1970-09-09 1974-02-28 Azolindolines and azolindoline dyestuffs Expired - Lifetime US3959306A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US05/446,892 US3959306A (en) 1970-09-09 1974-02-28 Azolindolines and azolindoline dyestuffs

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DT2044620 1970-09-09
DE19702044620 DE2044620A1 (en) 1970-09-09 1970-09-09 Azole indolines and azole indoline dyes
DE2044619A DE2044619C3 (en) 1970-09-09 1970-09-09 Basic azolindoline dyes, processes for their production and their use for dyeing and printing organic fiber materials
US00179181A US3840552A (en) 1970-09-09 1971-09-09 Azolindolines and azolindoline dyestuffs
US05/446,892 US3959306A (en) 1970-09-09 1974-02-28 Azolindolines and azolindoline dyestuffs

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US00179181A Division US3840552A (en) 1970-09-09 1971-09-09 Azolindolines and azolindoline dyestuffs

Publications (1)

Publication Number Publication Date
US3959306A true US3959306A (en) 1976-05-25

Family

ID=27431125

Family Applications (1)

Application Number Title Priority Date Filing Date
US05/446,892 Expired - Lifetime US3959306A (en) 1970-09-09 1974-02-28 Azolindolines and azolindoline dyestuffs

Country Status (1)

Country Link
US (1) US3959306A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140183413A1 (en) * 2012-12-28 2014-07-03 Dow Global Technologies Llc Quinoline-benzoxazole derived compounds for electronic films and devices

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3449330A (en) * 1964-09-01 1969-06-10 Ciba Ltd Azole derivatives
US3468619A (en) * 1964-05-12 1969-09-23 Bayer Ag Methine dyestuffs

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3468619A (en) * 1964-05-12 1969-09-23 Bayer Ag Methine dyestuffs
US3449330A (en) * 1964-09-01 1969-06-10 Ciba Ltd Azole derivatives

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140183413A1 (en) * 2012-12-28 2014-07-03 Dow Global Technologies Llc Quinoline-benzoxazole derived compounds for electronic films and devices
US9246108B2 (en) * 2012-12-28 2016-01-26 Dow Global Technologies Llc Quinoline-benzoxazole derived compounds for electronic films and devices

Similar Documents

Publication Publication Date Title
EP0318294B1 (en) Dimeric and trimeric cationic dyes
US4354970A (en) Indoline coupled isothiazole azo dyes
US3804823A (en) Heterocyclic containing monoazo compounds
US4384973A (en) Dimethine compounds of the coumarin series, a process for their preparation and their use as luminous dyestuffs
US3704302A (en) Certain cumarin quinazolinones
US4288589A (en) Cationic dyes
US3932446A (en) Quaternized 6-diethylamino-2-[benzimidazolyl-(2)]benzofuran
GB2026524A (en) Cationic dyes
US3985763A (en) Oxazolyl-acetic acid derivatives and oxazolyl-coumarines
US3840552A (en) Azolindolines and azolindoline dyestuffs
US3959306A (en) Azolindolines and azolindoline dyestuffs
US3828035A (en) Production of oxazine dyes with arylamino groups
US4016172A (en) Azolindolines and azolindoline dyestuffs
US3963747A (en) Basic arylmercaptonaphtholactam dyes
US3968119A (en) Vic-triazole compounds
US4009165A (en) Naphtholactam dyes
US4914190A (en) Tricyanovinyl-N,N-disubstituted anilines as disperse dyes
KR100296572B1 (en) dyes
US3950340A (en) Quinazoline dyes
US3941780A (en) Coumarin compounds
US3954743A (en) Coumarin and coumarinimide derivatives
US4271293A (en) Benzofuranyl-benzimidazoles
US3985772A (en) 3-Amidinocoumarin dyes
US4246404A (en) Basic indoline dyestuffs
US3635957A (en) Styryl dyes